Decorative material

ABSTRACT

A decorative material D having an intermediate resin layer and a surface protective layer comprising a crosslinked resin, the layers being laminated in this order on a substrate  1 , wherein the temperature dependency characteristics of loss elastic modulus E″ (a measuring frequency of 10 Hz) determined by a dynamic viscoelasticity method of the intermediate resin layer has a peak at least at a temperature under room temperature Tr. Further, it is preferable that the value of storage elastic modulus E″ is in a range of 1×10 7  to 2×10 9  Pa in the region of the room temperature. Also, it is preferable that loss elastic modulus E″ has the peak Pb in the temperature range over the room temperature.

BACKGROUND OF THE INVENTION

The present invention relates to decorative materials to be used forbuilding interior materials such as walls, surface materials offurniture and fixture such as doors and vehicle interior materials, andparticularly, to decorative materials which show excellent abrasionresistance because of their structure having a surface protective layercomprising a crosslinked resin.

Heretofore, decorative materials, such as decorative sheets, forapplications such as those described above are usually required to haveabrasion resistance. Thus, decorative materials whose surface protectivelayers are formed from two-component curing urethane resin paints,ionizing-radiation-curing resin paints and the like are practically usedtoday.

(1) For example, JP-B 49-31033 and JP-B 4-22694 disclose a decorativematerial wherein a pattern layer is formed on a substrate by printingand then a surface protective layer is further formed, the surfaceprotective layer comprising a resin resulting from a procedurecomprising applying an ionizing-radiation-curing resin paint ofunsaturated polyester type, acrylate type or the like to form a coatingfilm, and then curing the film by crosslinking with electron beams.

(2) Furthermore, for the case where a greater abrasion resistance isrequired, the published specification of Japanese Patent No.2740943discloses the addition of spherical particles such as sphericalα-alumina as an abrasion reducing agent to an ionizing-radiation-curingresin forming a surface protective layer.

However, even though a surface protective layer is formed of acrosslinked resin like in the above (1), abrasion resistance can not beimproved beyond a certain limit and only insufficient abrasionresistance may be obtained. The addition of hard inorganic particles asan abrasion reducing agent to the resin of a surface protective layerlike in the above (2) can improve abrasion resistance, but it may causea problem of generating a rough feeling in the surface of the surfaceprotective layer. Moreover, in the approach of the above (2), a problem,which is caused by the addition of the abrasion reducing agent, that aplate, a doctor blade and the like become easy to be worn during theformation of a surface protective layer is solved by the use ofspherical particles as an abrasion reducing agent. The use of such aspecific abrasion agent, however, may also cause a high cost problem.

SUMMARY OF THE INVENTION

The problem to be solved by the present invention is to provide to adecorative material with excellent abrasion resistance.

In order to solve the above problem, the decorative material of thepresent invention has a structure, that is, a decorative materialcomprising an intermediate resin layer and a surface protective layerincluding a crosslinked resin, the layers being laminated in this orderon a substrate, wherein a temperature dependency characteristic at ameasuring frequency of 10 Hz of loss elastic modulus determined by adynamic viscoelasticity method of the intermediate resin layer has apeak at least at a temperature lower than room temperature.

If, as described above, an intermediate resin layer whose dynamicviscoelastic characteristic is specified to have a peak of loss elasticmodulus in the region under room temperature is provided, an excellentabrasion resistance can be achieved without adding any abrasion reducingagent such as inorganic particles to a surface protective layer. This isprobably because the intermediate resin layer which became moderatelysoft at room temperature where an abrasion stress is added serves as acushion. In other words, it is probable that when an adequate elasticrestoring force is applied and simultaneously an external force(abrasion stress) that wears a surface is applied to a surfaceprotective layer, an intermediate layer underlying the surfaceprotective layer absorbs and relieves the external stress by dispersingthe external stress to a large area (volume) to reduce it and furtherconverting it to heat to dissipate, and as a result, the surfaceprotective layer becomes difficult to be worn and its abrasionresistance is improved. For this reason, the necessity of addingabrasion reducing agents such as inorganic particles to the surfaceprotective layer may be eliminated depending upon the degree of abrasionresistance required and it will become possible to avoid a rough feelingof a surface and abrasion of plates occurring during the formation of asurface protective layer, which would occur when abrasion reducingagents were added.

Moreover, the decorative material of the present invention may furtherhave a structure where the value of storage elastic modulus determinedby a dynamic viscoelasticity method of the intermediate resin layer is1×10⁷ to 2×10⁹ Pa in the range of room temperature, based on theabove-mentioned structure.

By adopting the structure of specifying the dynamic viscoelasticcharacteristics also about the storage elastic modulus, excellentabrasion resistance can be obtained more certainly without adding anyabrasion reducing agent such as inorganic particles to the surfaceprotective layer. This is probably because an intermediate layer can beprovided with such a moderate elastic restoring force that a surfaceprotective layer is prevented from excessive deformation and a surfacelayer is allowed to recover from its deformation and the surfacehardness of the surface protective layer is maintained.

Moreover, the decorative material of the present invention may furtherhave a structure where the temperature dependency characteristic at ameasuring frequency of 10 Hz of loss elastic modulus determined by thedynamic viscoelasticity method of the intermediate resin layer furtherhas a peak at a temperature higher than room temperature.

By adopting the structure of specifying to have a peak of loss elasticmodulus also in the temperature region higher than that where decorativematerials are practically used, excellent abrasion resistance can beobtained more certainly without adding any abrasion reducing agent suchas inorganic particles to the surface protective layer. This is probablybecause the peaks of the temperature dependency characteristic of losselastic modulus appearing, respectively, at a temperature under roomtemperature and at a temperature over room temperature make storageelastic modulus at room temperature easy to fall within a moderateregion, thereby providing to the intermediate resin layer such amoderate elastic restoring force that the surface protective layer isprevented from excessive deformation and a surface layer is allowed torecover from its deformation and the surface hardness of the surfaceprotective layer is maintained.

According to the decorative material of the present invention, anexcellent abrasion resistance can be obtained due to the intermediateresin layer having a specific dynamic viscoelastic characteristic ofhaving a peak of loss elastic modulus under room temperature. For thisreason, for some abrasion resistance required, it is not necessary toadd abrasion reducing agents such as inorganic particles into a surfaceprotective layer. For this reason, the necessity of adding abrasionreducing agents such as inorganic particles to the surface protectivelayer may be eliminated depending upon the degree of abrasion resistancerequired and it will become possible to avoid a rough feeling of asurface and abrasion of plates at the formation of the surfaceprotective layer, which would occur when abrasion reducing agents wereadded.

Furthermore, by specifying the dynamic viscoelastic characteristic ofthe intermediate resin layer to a specific storage elastic modulus,adequate elastic restoring force required for improving abrasionresistance and for maintaining surface hardness is obtained andtherefore the above-mentioned effect (1) can be obtained more certainly.

In addition to the above (1) or (2), it becomes easy to obtain adequateelasticity restoring force required for improving abrasion resistanceand for maintaining surface hardness also by specifying the loss elasticmodulus of the intermediate resin layer to be the dynamic viscoelasticcharacteristics having a peak also at a temperature over roomtemperature. Therefore, the above-mentioned effect (1) can be obtainedmore certainly.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 includes a sectional view illustrating one embodiment of thedecorative material of the present invention and an explanatory viewwhich schematically illustrates the dynamic viscoelastic characteristics(loss elastic modulus E″ and storage elastic modulus E′) of theintermediate resin layer.

FIG. 2 is a sectional view illustrating another embodiment of thedecorative material of the present invention.

FIG. 3 is a sectional view illustrating still another embodiment of thedecorative material of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the embodiments will be described about decorative materialof the present invention.

[Outline]

FIG. 1A is a sectional view showing the reference structure of thedecorative material of the present invention. The decorative material Dof the present invention has a structure where an intermediate resinlayer 2 having the above-mentioned specific dynamic viscoelasticcharacteristic and a surface protective layer 3 made up of a crosslinkedresin are laminated in this order on a substrate 1. The intermediateresin layer 2 is a resin layer disposed between the substrate 1 and thesurface protective layer 3 and the intermediate resin layer may have amultilayer structure comprising a plurality of layers having differentfunctions according to the application, physical properties required,etc. of the decorative material.

Examples of such a multilayer structure include a structure, like thedecorative material D illustrated using a sectional view in FIG. 2,wherein in the structure where an intermediate resin layer 2 having theabove-mentioned specific dynamic viscoelastic characteristic and asurface protective layer 3 made up of a crosslinked resin are laminatedon a substrate 1, the intermediate resin layer 2 is constituted of threelayers, a sealer layer 4, a pattern layer 5 and a primer layer 6,sequentially from the side of the substrate 1.

FIG. 1B is an explanatory view schematically illustrating theabove-mentioned specific dynamic viscoelasticity characteristic of anintermediate resin layer. FIG. 1(B) is a chart obtained by measuring,for the intermediate resin layer, temperature dependency characteristicof loss elastic modulus E″ and storage elastic modulus E′ by a dynamicviscoelasticity method at a measuring frequency of 10 Hz. In the presentinvention, the dynamic viscoelastic characteristic is adjusted so thatthe temperature dependency characteristic of loss elastic modulus E″ hasa peak Pa at a temperature under room temperature Tr. Moreover, thischart also shows a desirable case where the temperature dependencycharacteristic of loss elastic modulus E″ has also a peak Pb at atemperature over room temperature Tr. Furthermore, the chart alsocontains a temperature dependency characteristic of storage elasticmodulus E′ measured under the same conditions. This is also a desirablecase where the storage elastic modulus E′ desirably falls within theoptimal region R in which the values in the region of room temperatureTr are from 1×10⁷ to 2×10⁹ Pa.

As mentioned above, specifying the loss elastic modulus E″ or thestorage elastic modulus E′ as well as E″ of the intermediate resin layerto specific conditions can improve abrasion resistance of a decorativematerial (a surface protective layer) through the viscoelastic behaviorof the intermediate resin layer. It is to be noted that although suchimprovement in abrasion resistance can be obtained by a structure whereno abrasion reducing agent is added to the surface protective layer,abrasion reducing agents or the like may be added to the surfaceprotective layer when further improvement in abrasion resistance isrequired.

Hereinafter, each layer will be explained in more detail sequentiallyfrom a substrate.

[Substrate]

The substrate 1 has no particular limitations. For example, thesubstrate may have an optional configuration such as a sheet, a board, athree-dimensional object and the like depending upon the application ofthe decorative material. The material thereof is also optional.

The sheet is exemplified by paper, a resin sheet, non-woven fabric andmetallic foil. Specifically, examples of the paper include tissue paper,kraft paper, titanium paper, high-grade paper, linter paper, barytapaper, parchment paper, glassine, vegetable parchment paper, paraffinpaper, paperboard, coated paper, art paper, Japan paper and thoseimpregnated with resins such as acrylic resin, urethane resin andstyrene-butadiene rubber. Examples of the non-woven fabric include thosecomprising fibers of resin such as polyester resin and acrylic resin,inorganic fibers such as glass, carbon and asbestos. The resin sheet isexemplified by resin sheets (films) comprising resin such as polyolefinresins such as polyethylene, polypropylene, polybutene,polymethylpentene, ethylene-propylene copolymers,ethylene-propylene-butene copolymers and olefin-based thermoplasticelastomers, acrylic resins such as polymethyl (meth)acrylate, polybutyl(meth)acrylate, methyl (meth)acrylate-styrene copolymers and methyl(meth)acrylate-butyl (meth)acrylate copolymers, provided that “(meth)acrylate” means “acrylate or methacrylate”, polyester resins such aspolyethylene terephthalate, polybutylene terephthalate, polyethylenenaphthalate, polyallylate, ethylene terephthalate-isophthalatecopolymers and polyester-based thermoplastic elastomers, vinyl-basedresins such as polyvinyl chloride, polyvinylidene chloride and polyvinylalcohol, styrene-based resins such as polystyrene andacrylonitrile-butadiene-styrene copolymers (ABS resins), cellulosetriacetate, cellophane and polycarbonate. Examples of the metallic foilinclude metallic foils made up of aluminum, iron, stainless steel andcupper. Alternatively, laminates having two or more layers comprisingthe same kind or different kinds of sheets selected from theabove-listed various sheets.

As the board, woody boards, inorganic ceramics boards, resin boards,metallic boards and the like are mentioned. Specifically, the woodyboards are exemplified by wood veneers, plywoods, laminate woods,particle boards and middle density fiber board (MDF) formed of wood(including bamboo) suchas Japan cedar, pine, keyaki, oak, lauan, teak,melapi and bamboo. Examples of the inorganic ceramics boards includeinorganic non-metallic boards such as cement boards e.g., gypsum boards,gypsum slag boards, calcium silicate boards, asbestos slate boards, ALC(autoclaved light-weight concrete) boards and blow-extruded cementboards, pulp cement boards, asbestos cement boards, wood chip cementboards, GRC (glass fiber reinforced concrete) boards, ceramic boardsformed of earthenware, porcelain, stoneware, terra-cotta, glass andenameled ware. The resin boards are exemplified by resin boards such asthose formed of thermosetting resins, e.g., phenol resins, urea resins,unsaturated polyester resins, urethane resins, epoxy resins and melamineresins as well as a variety of thermoplastic resins described as theabove-mentioned material for resin sheets, and so-called FRP (fiberreinforced plastic) boards such as those obtained by impregnatingvarious kinds of fibrous substrates, such as glass fiber non-wovenfabric, cloth and paper, with resin such as phenol resins, urea resins,unsaturated polyester resins, urethane resins, epoxy resins, melamineresins and diallyl phthalate resin and curing the resins to combine thesubstrates and the resins. The metallic boards are exemplified by ironboards, zinc-plated steel board, polyvinyl chloride sol coated steelboards, aluminum boards and copper boards.

Examples of the three-dimensional object include columnar objects andobjects of other configurations made up of the various kinds of materiallisted for the above-mentioned boards. For example, columnar woods,three-dimensional resin moldings and the like are mentioned.

The decorative material is a decorative sheet when the substrate is asheet. More particularly, when the sheet, which is a substrate, ispaper, the decorative material is a decorative paper. Moreover, when thesubstrate is a board, it is a decorative board and when the substrate isa three-dimensional object, the decorative material is a decorativemember or a decorative product.

[Intermediate Resin Layer]

The intermediate resin layer 2 is a resin layer which is disposedbetween the substrate 1 and the surface decorative layer 3 and, in thepresent invention, whose dynamic viscoelastic characteristic isspecified. The resin to be used for the intermediate resin layer may be,with no particular limitations, any resin which satisfies theabove-mentioned dynamic viscoelastic characteristic specified in thepresent invention. For example, it may be either thermoplastic resin orcurable resin. It, therefore, is recommended to use, as the resin of theintermediate resin layer, a resin satisfying the specific dynamicviscoelastic characteristic according to application and physicalproperties required after a suitable selection from known resinmaterials.

As for the dynamic viscoelastic characteristic of the intermediate resinlayer, the abrasion resistance of a decorative material produced by asurface protective layer can be enhanced by at least allowing losselastic modulus E″ (or a temperature dependency characteristic thereof)to have a peak under room temperature. On the other hand, as for thesurface hardness the surface of a decorative material is usuallyrequired to have, a surface protective layer itself in which acrosslinked resin is used can exhibit an effect to some extent. Ifallowing loss elastic modulus E″ to have a peak under room temperaturemakes the intermediate resin layer too soft in the room temperatureregion, affecting the surface hardness to lower it, the shortageproduced can be compensated by means of further specifying the dynamicviscoelastic characteristic of the intermediate resin layer so that thevalue of storage elastic modulus E′ at room temperature falls within aspecific range. Furthermore, in addition to this, allowing the losselastic modulus E″ to have another peak over room temperature can makeit easier to bring the values of the storage elastic modulus E′ at roomtemperature within a specific range. Alternatively, it is also possibleto bring the values of the storage elastic modulus E′ at roomtemperature by allowing the loss elastic modulus E″ to have a peak overroom temperature (in addition to another peak under room temperature)without specifying the storage elastic modulus E′.

The storage elastic modulus E′ is preferably brought within the range offrom 1×10⁷ to 2×10⁹ Pa and is more preferably brought within a moredesirable range of from 2×10⁷ to 2×10⁹ Pa. This is because a storageelastic modulus E′ of less than 1×10⁷ Pa will cause the intermediateresin layer to deform in a greater degree and may result in reduction ofsurface hardness produced by the surface protective layer-and indecrease in the effect of improving abrasion resistance.

It is to be noted that such a dynamic viscoelastic characteristicintroduces rubber-elastic factors to the intermediate resin layer, butdoes not make it completely rubber-elastic. The substances generallycalled rubber only have storage elastic modulus E″ less than theabove-mentioned range in order. If the intermediate resin layer is toosoft like rubber, too much deformation may occur and no abrasionresistance improving effect is obtained.

Incidentally, the temperature dependency characteristics of the losselastic modulus E″ and the storage elastic modulus E′ of theintermediate resin layer in the dynamic viscoelasticity method measuredat a measuring frequency of 10 Hz can be measured using a commerciallyavailable dynamic viscoelasticity measurement apparatus, for example,“Rheogel-E4000” manufactured by UBM. In general, the sample deformationmode is classified, based on the mode of applying force to samples to bemeasured, into a bend mode, a tensile mode, a twist mode and a shearmode. In the present invention, the tensile mode is used from theconsideration to the form of the samples to be measured (a film form).In the practical measurement, the conditions were set as follows:

-   -   Vibration applied: sinusoidal wave of a frequency of 10 Hz    -   Stress: 5 μm    -   Temperature elevation rate: 3° C./min    -   Capturing temperature: every 2° C.    -   Measuring temperature range: from −50° C. to 120° C.        The measuring samples used were prepared by pouring a coating        liquid for forming an intermediate resin layer into a weighing        dish of polypropylene with a flat bottom and drying it to form a        coating film having an intermediate resin layer only. The size        of the measuring samples is for example, a rectangle about 100        μm thick, 20 mm long and 5 mm wide. As for the measuring        frequency, measurement may inherently be conducted at any        frequency as long as the presence of peaks of the temperature        dependency of abrasion resistance and loss elastic modulus and a        co-relation with the storage elastic modulus can be clarified        and the measurement can be conducted easily. However, the        present invention adopts a measuring frequency of 10 Hz since        the measurement at a frequency of 10 Hz has spread in the        organic macromolecule field, it is easy to get measurement        apparatus and the co-relation with abrasion resistance actually        becomes clear at a frequency of 10 Hz.

It is probably possible to adopt a relationship between a so-calledglass transition temperature Tg and room temperature Tr (Tg≦Tr) as anindex of softness of a resin at room temperature (region), this does notpermit accurate product design. This is because, based on a variety oftests and studies, the loss elastic modulus E″ and the storage elasticmodulus E′ by the dynamic viscoelasticity method adopted in the presentinvention are measured under the application of external force as afunction of time and, therefore, situations closer to the practical useconditions (of decorative materials) are reflected to the abrasionphenomena caused by the external force, and accordingly, it becomespossible to achieve accurate product design. In contrast, since a glasstransition temperature is usually obtained using a DSC (a differentialscanning calorimeter) which measures without applying external force, abehavior caused by dynamic external force is not reflected to themeasured results. Moreover, generally, a peak temperature of losselastic modulus does not agree with a glass transition temperature. Forexample, specifically, a certain resin has a glass transitiontemperature of 18° C., but a peak temperature of its loss elasticmodulus E″ under room temperature is 67° C. When the lower limit of roomtemperature is temporarily defined as 20° C., if a glass transitiontemperature lower than room temperature is acceptable, this resin willbecome adoptable. However, this resin can not improve abrasionresistance actually. The fact that the temperature of the peak Pa of theloss elastic modulus of this resin under room temperature is 67° C.,which is not lower than room temperature, is reflected actually. “Roomtemperature” used in the present invention means a temperature at whicha decorative material is used and is a ranged temperature, for example,from 0° C. to 70° C. This is because the environmental temperature atwhich decorative materials are used varies widely depending upontemperature change in the daytime, seasonal variation, and the area inwhich decorative materials are used (a cold district, subtropics and thelike.) Moreover, in general, decorative materials are finally usedinside structures such as rooms and vehicles. However, before executionof construction, they are exposed to temperature changes in carriers,warehouses and the like. Including such cases, the “room temperature”means environmental temperatures at which decorative materials are used.Therefore, the “room temperature” should not be defined as only onetemperature (for example, 25° C.), but is defined as ranged temperatureregion. However, it is not necessary to make the temperature regioncorrespond to all temperature changes. It is possible to determine thetemperature range of room temperature based on the lower and upperlimits of the temperatures which should be considered under theenvironment where the desired decorative material is employed. The resinfor the intermediate resin layer of the present invention is selectedaccording to the designed desired value of the determined temperaturerange. Accordingly, the maximum and the minimum of room temperature mayvary depending upon the application of a decorative material. Forexample, if a decorative material is used as an interior material of avehicle, better results can be obtained by determining thecharacteristics of an intermediate resin layer using room temperatureparticularly having a relatively higher upper limit than that for indoorapplications. Needless to say, if the resin to be used for anintermediate resin layer or its cost permit, the characteristics of theintermediate resin layer may also be determined through setting roomtemperature such as provides a relatively wide temperature range aftertaking various applications widely into consideration. Furthermore, inpractical product design, both ends of the lower limit or the upperlimit may be neglected so that the temperature range is reduceddepending upon frequency (possibility) of the occurrence of temperaturesto reach the lower limit and the upper limit under the use environmentand the strength of abrasion force applied at the time and frequency ofeach occurrence, from the relationship with cost or the like. Forexample, in the case of designing for usual indoor applications inJapan, it is recommended to set the lower limit of room temperature tobe 10° C. and the upper limit to 50° C. Examples, which will bedescribed later, are those designed according to this room temperaturesetting.

Incidentally, for making a resin to be adopted for the intermediatelayer to have a peak of its loss elastic modulus E″ at a temperatureunder room temperature or to have a peak at a temperature over roomtemperature, there is a general tendency that use of an aliphatic systemas the molecular chain structure of the resin decreases a peaktemperature or that use of an aromatic system increases a peaktemperature. Moreover, the molecular weight (polymerization degree) ofthe resin must exceed a certain value (for example, a polymerizationdegree of 500) for clear appearance of peaks of the loss elastic modulusE″. However, it does not have very much to do with a peak temperature.As mentioned above, the loss elastic modulus E″ can be controlled atwill by molecule designing the molecular chain structure of the resinappropriately.

Moreover, when mixing two resins having different peak temperatures ofloss elastic modulus E″, microscopically complete mixing of both resinsmay result in fusion or disappearance of their peaks. However, when theboth resins are mixed while being in microscopic phase separation, theirpeaks may remain at the different temperatures. Therefore, in order tocause the loss elastic modulus E″ of the intermediate layer to have botha peak Pa under room temperature and a peak Pb over room temperature, itis also possible to mix two or more kinds of resins. In other words, itis also possible to use a mixed resin in which a resin having a peak Paunder room temperature in its loss elastic modulus E″ and a resin havinga peak Pb over room temperature in its loss elastic modulus E″.

That the resin used for the intermediate resin layer is not particularlylimited as long as it satisfies the above-mentioned dynamic viscoelasticcharacteristic and may, for example, be thermoplastic resins and curableresins was stated previously. Specific examples thereof includethermoplastic resins such as acrylic resin, polyester resin,styrene-butadiene rubber (SBR) and thermoplastic urethane resin andcurable resins such as two-component curing type urethane resin, whichmay be used either alone or as mixtures of two or more of them.Particularly, polyester resin is suitable based on the fact that it isone of the resins easy to be adjusted their dynamic viscoelasticcharacteristic through the selection of the type and formulation of apolyhydric alcohol and a polybasic acid to be used as raw materials.

It is to be noted that using and crosslinking a curable resin is moredesirable than using a thermoplastic resin (or crosslinking and thenusing as a curable resin is more desirable than using as a thermoplasticresin) because abrasion resistance is improved together with solventresistance and heat resistance. Although crosslinking can be achieved byknown methods, it can be done by using isocyanate as a crosslinkingagent or by a method in which by allowing a resin molecular to have anacryloyl group therein (for example, polyesteracrylate resulting fromreacting acrylic acid, methacrylic acid or the like with polyester resin(prepolymer) or various kinds of acrylate-based prepolymers) and alsousing an ionizing-radiation-curing resin of acrylate type or the likefor the surface protective layer, the aforesaid acryloyl group is curedsimultaneously with the curing of the surface protective layer withiodizing-radiation irradiation. Alternatively, it is also possible toallow a resin molecule to have an active-hydrogen-containing group suchas a hydroxyl group therein (for example, various kinds of polyols usedas the main component of two-component curing type urethane resin, suchas polyester polyol, acrylic polyol, polyether polyol, polycarbonatepolyol and polyurethane polyol) or allow it to have an isocyanate groupor the like, and to use a urethane resin of two-component curing type orthe like for the surface protective layer, thereby curing theintermediate resin layer simultaneously with the curing of the surfaceprotective layer on heat or the like. It is to be noted that since apolyester resin has a remaining hydroxyl group as a reaction residualgroup, it can be used as a main component of a two-component curing typeurethane resin.

The amount of a crosslinking agent to be added varies depending on theresin system, the type of the crosslinking agent and the like, but isusually approximately from 1 to 10 parts by weight based on 100 parts byweight of the resin (the main component).

Examples of isocyanate to be used include polyisocyanates such asaromatic isocyanates, e.g., 2,4-tolylene diisocyanate, xylenediisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethanediisocyanate, or aliphatic (or alicyclic) isocyanates such as1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenatedtolylene diisocyanate and hydrogenated diphenylmethane diisocyanate,etc. Alternatively, adducts or multimers of the above-mentionedisocyanates can be employed. These are exemplified by adducts oftolylene diisocyanate, a trimer of tolylene diisocyanate, adducts of1,6-hexamethylene diisocyanate, and the like. Aliphatic (or alicyclic)isocyanates are preferable to aromatic isocyanates from the viewpointsof weatherability and heat yellowing resistance.

The intermediate resin layer can be formed by known coating filmformation methods such as coating or printing with a coating liquid (orink) comprising a solution containing the above-mentioned resindissolved or a dispersing liquid containing the above-mentioned resindispersed. When the intermediate resin layer is formed on a fullsurface, it can be formed by coating methods such as gravure coating androll coating. Alternatively, when it is formed in a pattern or on thefull surface, it can be formed by printing methods such as gravureprinting, silkscreen printing, offset printing and gravure offsetprinting. Also in the case of making the coating liquid (or ink)aqueous, isocyanate crosslinking can be achieved by, for example,causing an isocyanate to be a block isocyanate, volatizing and dryingwater, which is used as a solvent or a dispersing medium, followed byreleasing the block of isocyanate on heating.

The thickness of the intermediate resin layer varies depending onapplications, physical properties required and the like, but it isusually set to be approximately from 1 to 10 μm as the total thicknessin both single-layered structure and multi-layered structure.

Incidentally, when a desired design expression is satisfied by only twolayers of the substrate and the surface protective layer, it is alsopossible to form the intermediate resin layer as a mere colorlesstransparent resin layer containing no coloring agents or the like.However, in usual, the intermediate resin layer is formed as a layerhaving functions such as decoration. For example, as illustrated in FIG.2, the intermediate resin layer maybe formed as a layer combining layersof various kinds of functions other than the improvement in abrasionresistance, such as a sealer layer 4, a pattern layer 5 and a primerlayer 6. In the combination with such functional layers, theintermediate resin layer may be combined with one or two or morefunctional layers. FIG. 1 shows an example of a multilayer structurewherein the intermediate resin layer is combined with three layers.

The sealer layer 4 is a layer which is provided for preventing a coatingliquid or an ink from being absorbed into the substrate, resulting inthe reduction in the coating thickness or for preventing a coating filmor a ink film from generating luster unevenness caused by surfaceunevenness of the substrate when the substrate is made of paper, wood orthe like so that its surface becomes a rough surface or showspermeability.

Furthermore, a coloring agent may be added to the intermediate layer(including a layer combined with various kinds of functional layers) toform a colored layer, a concealment layer, a colored concealment layerand the like, which are formed in a full surface.

Moreover, when adding a coloring agent to the intermediate resin layerand also forming the layer in a pattern, it can be formed as a patternlayer. Considering the original purpose of the intermediate resin layer,it is preferable not to form such layers scattered. In the case of apattern layer of multicolor printing, it is also possible to form alayer lying in almost a full surface or in a full surface without beingscattered as a whole as the result of overlapping even if the layers ofeach color exist separately.

When the intermediate resin layer has a multilayered structure, thelayer contacting the surface protective layer can be a layer servingalso as a primer layer for enhancing adhesion to the surface protectivelayer. Such a primer layer is formed also for the purpose of enhancingadhesion between different kinds of layers including the substrate inaddition to the purpose of enhancing adhesion to the surface protectivelayer. Therefore, when the intermediate resin layer in a multilayeredstructure contacts with the substrate, the layer that contacts with thesubstrate can be combined with a primer layer to the substrate. Examplesof such cases include polyolefin resin sheets, which generally show pooradhesiveness.

Incidentally, the intermediate resin layer is required only to bedisposed between the substrate and the surface protective layer.However, when layers other than the intermediate resin layer (forexample, a pattern layer, a sealer layer and the like not combined withthe intermediate resin layer) are also disposed between the substrateand the surface protective layer, it is desirable that the intermediateresin layer is either a layer disposed immediately below the surfaceprotective layer with being contact with the surface protective layer ora layer dispose closer to the surface protective layer since a cushioneffect due to the intermediate resin layer is given directly to thesurface protective layer. Therefore, for example, a patter layer that isnot combined with the intermediate resin layer is preferably disposedbetween the intermediate resin layer and the substrate. In this case, ifthe adhesion is poor when the pattern layer and the surface protectivelayer directly contact, it is also possible to consider the intermediateresin layer to be a primer layer binding the pattern layer and thesurface protective layer.

Unless the expression of the previously mentioned specific loss elasticmodulus and storage elastic modulus are inhibited, known additives suchas extenders, e.g., silica, calcium carbonate and barium sulfate,ultraviolet absorbers such as benzotriazole, benzophenone and fineparticle cerium oxide, light stabilizers such as hindered amine typeradical scavenger, and heat stabilizers may be added to the intermediateresin layer for appropriately adjusting an aptitude for coating, anaptitude for printing and other properties.

Moreover, when a coloring agent is added to the intermediate resin layerto form a patter layer (including a full-surface colored solid layer),known coloring agents can be used as such a coloring agent. For example,inorganic pigments such as titanium white, zinc white, carbon black,iron black, iron oxide red, cadmium red, chrome yellow, titanium yellow,cobalt blue and ultramarine blue, organic pigments such as anilineblack, quinacridon red, polyazo red, isoindolinone yellow, benzidineyellow, phthalocyanine blue and indanthrene blue, glittering pigmentssuch as titanium dioxide-coatedmica, shell and scale-like powders ofbrass, aluminum and the like, or other dyes.

Any pattern is available as patterns to be expressed with a patternlayer combined with the intermediate resin layer or with a pattern layernot combined with the intermediate resin layer. Examples of such apattern include a woodgrain pattern, a stonegrain pattern, a texturepattern, a tile-like pattern, a brick-like pattern, a leather grainpatter, sand grain pattern, an aventurine pattern, characters, symbolsand a geometrical pattern, etc.

In the case of pattern layers not combined with the intermediate resinlayer, known resins may appropriately be employed as a binder resindepending upon physical properties required such as adhesiveness toother layers. For example, a single substance selected from or a mixturecontaining substances selected from cellulose-type resins such asnitrocellulose, cellulose acetate and cellulose acetate propionate,urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymers,polyester resin, alkyd resin and the like is used.

[Surface Protective Layer]

The surface protective layer 3 is a layer that becomes an outermostsurface layer and may be formed of a thermoplastic resin. However, thesurface protective layer is preferably formed of a curable resin thatcan produce a crosslinked resin since it can achieve good abrasionresistance. As such a curable resin, any known resin can be used and,for example, ionizing-radiation-curing resins, two-component curing typeurethane resins, epoxy resins, melamine resins and the like can be used.The surface protective layer can be formed by known coating methods suchas roll coating and gravure roll coating using a coating liquidcomprising one or two or more resins selected from the above-recitedresins. Alternatively, it may also be formed by full-surface solidprinting using known printing methods such as gravure printing andsilkscreen printing. The thickness of the surface protective layerdepends upon application, physical properties required and the like, butit is approximately from 1 to 30 μm.

The above-mentioned ionizing-radiation-curing resin is a compositioncruable by crosslinking with ionizing radiation. Specifically,compositions which result from suitable mixing of a prepolymer(including so-called oligomer) and/or monomer having a radicalpolymerizable unsaturated bond or a cationic polymerizable functionalgroup in the molecule and which are curable with ionizing radiation arepreferably employed. Such propolymer and/or monomer is used as a singlesubstance or a mixture of two or more sorts.

The aforesaid prepolymer or monomer comprises a compound having in itsmolecule a radical polymerizable unsaturated bond such as a(meth)acryloyl group and a (meth)acryloyloxy group, a cationicpolymerizable functional group such as an epoxy group, and the like. Inaddition, polyene/thiol-type prepolymers resulting from combination ofpolyene and polythiol can also be desirably used. It is to be notedthat, for example, the (meth)acryloyl group indicates an acryloyl groupor a methacryloyl group.

As a prepolymer having a radical polymerizable unsaturated group,polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate,melamine (meth)acrylate, triazine (meth)acrylate, silicon(meth)acrylate, etc. can be used. Those having a molecular weight ofapproximately from 250 to 100,000 are used.

Examples of the monomer having a radical polymerizable unsaturated groupinclude monofunctional monomers such as methyl (meth) acrylate,2-ethylhexyl (meth) acrylate and phenoxyethyl (meth)acrylate as a singleorganic-functions monomer and polyfunctional monomers such as diethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate, hexanedioldi(meth)acrylate, trimethylolpropane tri(meth)acrylate,trimethylolpropane ethylene oxide tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate,dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa(meth) acrylate.

Examples of the prbpolymer having a cationic polymerizable functionalgroup include epoxy resins such as bisphenol-type epoxy resins andnovolak-type epoxy resins, prepolymers of vinyl ether resins such asfatty acid-type vinyl ethers and aromatic type vinyl ethers.

Example of thiol include polythiols such as trimethylolpropanetrithioglycolate and pentaerythritol tetrathioglycolate. Examples ofpolyene include products resulting form addition of allyl alcohol toboth ends of polyurethanes made up of a diol and a diisocyanate.

Furthermore, when conducting crosslinking and curing with ultravioletrays or visible rays, a photopolymerization initiator is further addedto the above-mentioned ionizing-radiation curing resin. For resinshaving a radical polymerizable unsaturated group, an acetophenone, abenzophenone, a thioxanthone, benzoin and a benzoin methyl ether areused alone or after mixing as a photopolymerization initiator. Forresins having a cationic polymerizable functional group, an aromaticdiazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, ametallocene compound, a benzoin sulfonate, etc. can be used alone or inthe form of mixture as a photopolymerization initiator. The amount ofthese photopolymerization initiators to be added is approximately from0.1 to 10 parts by weight based on 100 parts by weight of anionizing-radiation curing resin.

As the ionizing radiation, electromagnetic waves or charged particleswhich have energy sufficient to cause molecules in ionizingradiation-curable resins (compositions) to cure. Although the usuallyused is ultraviolet radiation or electron beam, it is also possible touse visible radiation, X-ray, charged particle beam, etc. As anultraviolet radiation source, light sources such as an extra-highpressure mercury vapor lamp, a high pressure mercury vapor lamp, a lowpressure mercury vapor lamp, a carbon arc light, a black light and ametal halide lamp and the like are used. As wavelength of ultravioletradiation, a wavelength region of from 190 nm to 380 nm is usuallymainly used. Electron beam sources usable herein include variouselectron beam accelerators, such as a Cockcroft-Walton accelerator, avan de Graaff accelerator, a resonance transformer accelerator, aninsulated core transformer accelerator, a linear accelerator, aDyamitron accelerator, and a high frequency accelerator. What is usedcan irradiate electrons having an energy of 100 to 10000 keV, preferably100 to 300 keV.

Moreover, to the above-mentioned ionizing radiation-curable resins, itis also possible to add thermoplastic resins such as vinylchloride-vinyl acetate copolymer, vinyl acetate resin; acrylic resin andcellulose resin as needed.

Furthermore, to the above-mentioned ionizing radiation-curable resins,it is also possible to further add various additives. Examples of suchadditives include extenders (fillers) comprising fine particles ofcalcium carbonate, bariumsulfate, silica, alumina and the like, coloringagents such as dyes and pigments.

Moreover, the decorative material of the present invention does not needabrasion reducing agents since it has an improved abrasion resistancedue to the intermediate resin layer. However, when a better abrasionresistance is required and the influences of a rough feeling ofsurfaces, abrasion of doctors, abrasion of boards and the like can beneglected, abrasion reducing agents comprising hard inorganic particlessuch as alumina (α-alumina, etc.), silica, glass, silicon carbide, boroncarbide and diamond, lubricants such as silicon resin, silicon oil,fluororesin, fluorine-modified resin, vegetable wax, montan wax andparaffin wax may also be added to the resin of the surface protectivelayer.

The abrasion reducing agent is an additive by a physical approach whoseparticle itself has a hardness (for example, Vickers hardness) greaterthan that of the resin of the surface protective layer and which impartsthe surface protective layer. resistance to external stress through sucha hardness to improve abrasion resistance.

The lubricant is an additive by a physical chemical approach whichreduces a coefficient of dynamic or static friction to improve abrasionresistance.

The surface protective layer can be formed by applying a coating liquidcontaining a resin such as those mentioned above by conventionally knowncoating methods such as roll coating and flow coating. Alternatively, itcan be formed by full-surface printing by conventionally known printingmethods such as gravure printing.

[Adherend substrate]

The decorative material (especially, those in the form of decorativesheet such as decorative paper) of the present invention is used assurface decorative materials for being stuck on surfaces of a variouskinds of adherend substrates.

The adherend substances have no particular limitations. For example, thematerial of such adherend substrates include materials of inorganicnonmetallic type, metallic type, woody type, resin type, etc.Specifically, those of the inorganic nonmetallic type include inorganicmaterials such as those of non-pottery ceramic industry type, e.g.,paper-made cement, extruded cement, slag cement, ALC (autoclavedlightweight concret) and GRC (glass fiber reinforced concrete), pulpcement, woodchip cement, asbestos cement, calcium silicate, plaster andplaster slag, and ceramics, e.g., terra-cotta, earthenware, porcelain,stoneware, glass and enameled ware. Those of the metallic type includemetallic materials such as iron, aluminium and copper. Those of thewoody type include veneers, plywoods, particle boards, fiberboards,laminate woods, etc. made of Japan cedar, hinoki, oak, lauan, teak, etc.Those of the resin type include polypropylene, ABS resin and phenolresin.

The adherend substrate may have any configuration and, for exampl, flatpaltes, curved boards and multi-cornered prisms are available.

[Application]

The decorative material of the present invention has no particularlimitations in its application and is used for building interiormaterials such as walls, floors and ceilings, fixtures such as doors,door frames and window frames, fittings such as ceiling cornices andplinthes and furniture such as wardrobes and cabinets.

EXAMPLES

Hereafter, the present invention is further described by reference toExamples and Comparative Examples.

Example 1

For test and evaluation, decorative material D, which will be processedto a decorative paper of a structure shown in FIG. 3, was prepared asfollows.

First, on one side of an unbleached tissue paper (unimpregnated paper)having a weight of 30 g/m² as a substrate 1, an intermediate layer 2comprising three layers, a white colored solid layer 7 (it is also afull-surface solid layer in a pattern layer), a pattern layer 5 having afull-surface red pattern and a primer layer 6, was formed throughapplying the layers with a Meyer bar sequentially from the substrate inapplication amounts (on solid basis, hereafter the same) of 5 g/m², 2g/m² and 2 g/m², respectively. The three layers contained the same resincomponent. The resin used was, as shown in Table 1, a two-componentcurable urethane resin resulting from mixing 3 parts by weight of1,6-hexamethylene diisocyanate (HMDI) adduct as an isocyanate-basedcrosslinking agent and 100 parts by weight of a main componentcomprising a mixed resin of a (saturated) polyester resin (containinghydroxyl groups) [in the Table, this is abbreviated PES; hereinafter, [] at each occurrence is the same] and an unsaturated polyester resin(containing hydroxyl groups) [U-PES] in a weight ratio of 4 to 6.

As for a single-layered film-of the resin formed in a weighing dish ofpolypropylene resin, the dynamic viscoelastic characteristics of theabove-mentioned resin (in this case, a crosslinked cured resin) weremeasured using a dynamic viscoelasticity measurement apparatus(manufactured by UBM, “Rheogel-E4000”). The measurement was carried outin tensile mode while being vibrated in a 10 Hz sinusoidal wave underthe measuring conditions: a stress of 5 μm, a temperature elevation rateof 3° C./min, a capturing temperature of every 2° C., and a measuringtemperature range of −50° C. to 120° C. As the result, the temperaturedependency characteristic of loss elastic modulus E″ had a peak at −14°C., which is under room temperature (in a series of decorative materialsprepared, from 10° C. to 50° C. was defined as room temperature) andalso had another peak at 90° C., which is over room temperature.Moreover, storage elastic modulus E′ was 7×10⁷ to 2×10⁸ Pa in theabove-mentioned room temperature range.

Furthermore, a paint comprising an electron beam curable resin composedof 20 parts by weight of four-functional urethane acrylate prepolymer,40 parts by weight of three-functional urethane acrylate prepolymer and40 parts by weight of polyester acrylate oligomer was applied to theintermediate layer 2 with a Meyer bar so that its application amountbecame 5 g/m2, and subsequently the coating was crosslinked and cured bythe irradiation of electron beam under the conditions of 175 keV(s) and30 kGy (3 Mrad), thereby forming a surface protective layer 3 comprisinga cured resin to yield decorative material D.

Example 2

A decorative material was obtained in the same manner as Example 1except that in Example 1 the resin of the intermediate layer having thethree layer structure serving as a sealer layer, a pattern layer and aprimer layer was changed to an aqueous (saturated) polyester resin[aqueous PES] and no crosslinking agent was used. A peak temperature ofthe loss elastic modulus E″ of the above resin at temperatures underroom temperature is −31° C. and there are no peaks over roomtemperature. A value of storage elastic modulus E′ in the roomtemperature range was 2×10⁷ to 2×10⁸ Pa.

Example 3

A decorative material was obtained in the same manner as Example 1except that in Example 1 only the main component was used and acrosslining agent was not used as a resin of an intermediate layer asshown in Table 1. A peak temperature of the loss elastic modulus E″ ofthe resin (the non-crosslinked thermoplastic resin) at temperaturesunder room temperature became −10° C. and a peak temperature over roomtemperature became 6° C. A value of storage elastic modulus E′ in theroom temperature range was 2×10⁷ to 2×10⁸ Pa.

Example 4

A decorative material was obtained in the same manner as Example 1except that in Example 1, as a resin of an intermediate layer only a(saturated) polyester resin [PES] (the cross linking agent wasincorporated) was used as shown in Table 1. A peak temperature of theloss elastic modulus E″ of the resin (the crosslinked resin) attemperatures under room temperature became −10° C. and there was no peakat temperatures over room temperature. A value of storage elasticmodulus E′ in the room temperature range was 1×10⁷ to 2×10⁷ Pa.

Example 5

A decorative material was obtained in the same manner as Example 1except that in Example 1, as a resin of an intermediate layer an acrylicresin [AC (A)] (no crosslinking agent was used) was used as shown inTable 1. A peak temperature of the loss elastic modulus E″ of the resin(thermoplastic resin) at temperatures under room temperature became 6°C. and there was no peak at temperatures over room temperature. A valueof storage elastic modulus E′ in the room temperature range was 2×10⁸ to2×10⁹ Pa.

Example 6

A decorative material was obtained in the same manner as Example 1except that in Example 1, in place of the electron beam curable resin[EB] as a resin of a surface protective layer, a two-component urethaneresin [2-component PU] was used, the resin resulting from theincorporation of 12 parts by weigh of a crosslinking agent, the HMDIadduct, to 100 parts by weight of the main component, urethane polyol.

Comparative Example 1

A decorative material was obtained in the same manner as Example 1except that in Example 1, as a resin of an intermediate layer, a mixedresin composed of an acrylic resin [AC (B)] (having a composition ofresin different from that of the acrylic resin used in Example 5) and avinyl chloride-vinyl acetate copolymer [VC-VA] in a weight ratio of 5 to5 (no crosslinking agent was used) was used as shown in Table 1. Theloss elastic modulus E″ of the mixed resin (thermoplastic resin) had nopeaks at temperatures under room temperature, but there was a peak at51° C., which is over room temperature. A value of storage elasticmodulus E′ in the room temperature range was 6×10⁸ to 2×10⁹ Pa.

Comparative Example 2

A decorative material was obtained in the same manner as Example 1except that in Example 1, as a resin of an intermediate layer, anacrylurethane resin [ACU] was used (no crosslinking agent was used) asshown in Table 1. The loss elastic modulus E″ of the resin(thermoplastic resin) had no peaks at temperatures under or over roomtemperature, but there was a peak within the room temperature range (at31° C. A value of storage elastic modulus E′ in the room temperaturerange was 2×10⁷ to 1×10⁹ Pa.

Comparative Example 3

A decorative material was obtained in the same manner as Example 1except that the formation of an intermediate layer was omitted. TABLE 1Content of intermediate layer and evaluation results Intermediate layerEvaluation result Dynamic viscoelastic characteristics Resin of AbrasionComposition of resin *1 E* peak E* peak Value of E′ surface resistanceMain Crosslinking (<room (>room (in room temperature protective layerevaluation and loss Solvent component agent temperature) temperature)range) *2 (mg) resistance Examples 1 PES/U- NCO 3% −14° C. 90° C. 7 ×10⁷-2 × 10⁸ Pa EB ◯(11) ◯ PES = 4/6 2 Aqueous None −31° C. NONE 2 ×10⁷-2 × 10⁸ Pa EB ◯(14) X PES 3 PES/U- None −10° C. 60° C. 1 × 10⁷-2 ×10⁸ Pa EB ◯(14) X PES = 4/6 4 PES NCO 3% −10° C. NONE 1 × 10⁷-2 × 10⁷ PaEB ◯(9)  ◯ 5 AC(A) NONE    6° C. NONE 2 × 10⁸-2 × 10⁹ Pa EB ◯(11) X 6PES/U- NCO 3% −14° C. 90° C. 7 × 10⁷-2 × 10⁸ Pa 2-comp. PR ◯(9)  ◯ PES =4/6 Comparative 1 AC(B)NC- NONE NONE 51° C. 6 × 10⁸-2 × 10⁹ Pa EB  X(31)X Examples VA = 5/5 2 ACU NONE NONE*3 NONE 2 × 10⁷-1 × 10⁹ Pa EB  X(18)X 3 No intermediate layer EB X(16) X*1: PES = polyester resin (containing hydroxyl group); U-PES =unsaturated polyester resin; aqueous PES = aqueous polyester# resin; AC = acrylicresin [(A) and (B) are different in composition ofresin]; VC-VA = vinyl chloride-vinyl acetate copolymer; ACU # = acrylurethane resin; NCO (crosslinking agent) = adduct of 1,6-hexamethylenediisocyanate (HMDI)*2: EB = Electron beam curable resin; 2-comp PU = two-component curableurethane resin*3: There is a peak at 31° C. within the room temperature range.

Performance evaluation

Each of the decorative materials of Examples and Comparative Exampleswas stuck on a 3 mm thick Chinese veneer board, which was used as awoody substrate as an adherend substrate, with a double-sided adhesivetape to form a decorative panel, which was then evaluated. Theevaluation was performed about abrasion resistance and solventresistance in the following procedures.

(1) Abrasion resistance : Abrasion resistance was evaluated according toJIS K 6902 “Testing method for laminated thermosetting high-pressuredecorative sheets” and the abrasion resistance test of NEMA Standard.Specifically, using a Taber's abrader (manufactured by Toyo SeikiSeisaku-Sho, Ltd.), two abrasion losses [mg] after 10 rotations weremeasured using S42 abrasive paper by 9.81 N (1 kgf) of both wheelsloads. The evaluation was done based on the average of the measurements.

(2) Solvent resistance : The surface of the surface protective layer ofa decorative sheet was rubbed back and forth 200 times with a gauzecontaining methyl ethyl ketone under a load of 0.981 N (100 gf) andappearance change of the decorative material caused by the solvent wasvisually observed. A sample showing no change is judged good and thatshowing some changes is judged poor.

As the results of the above evaluation, the abrasion resistances in allExamples were good as shown in Table 1. However, those in allComparative Examples were poor. Namely, in Comparative Example 3, therewas no intermediate resin layer. In Comparative Example 2, even therewas an intermediate resin layer and its storage elastic modulus E′ was1×10⁷ to 2×10⁹ Pa in the room temperature range, the important losselastic modulus E″ had no peaks under room temperature. In ComparativeExample 1, the loss elastic modulus E″ had a peak, but the peak existedonly in the temperature range over room temperature.

On the other hand, although in all of the Examples and ComparativeExamples the surface protective layers were formed of a crosslinkedresin, the solvent resistance was poor in Examples 2, 3, 5 andComparative Examples 2 and 3 where the intermediate layers were formedof thermoplastic resin. However, it was good in Examples 1, 4 and 6where the intermediate layers were formed of crosslinked resin.Therefore, it is shown that it is desirable to form an intermediatelayer of a crosslinked resin for applications where solvent resistanceis required as well as abrasion resistance.

1-4. (cancelled)
 5. A decorative material comprising an intermediateresin layer and a surface protective layer including a crosslinkedresin, the layers being laminated in this order on a substrate, whereinthe temperature dependency characteristics at a measuring frequency of10 Hz of loss elastic modulus determined by a dynamic viscoelasticitymethod of the intermediate resin layer has a peak at least at atemperature lower than room temperature, and the intermediate resinlayer is in contact with the surface protective layer.
 6. The decorativematerial according to claim 5, wherein the value of storage elasticmodulus determined by a dynamic viscoelasticity method of theintermediate resin layer at a measuring frequency of 10 Hz is 1×10⁷ to2×10⁹ Pa in the range of room temperature.
 7. A decorative materialcomprising an intermediate resin layer and a surface protective layerincluding a crosslinked resin, the layers being laminated in this orderon a substrate, wherein the temperature dependency characteristics at ameasuring frequency of 10 Hz of loss elastic modulus determined by adynamic viscoelasticity method of the intermediate resin layer has apeak at least at a temperature lower than room temperature, and further,has a peak at a temperature higher than room temperature.
 8. Thedecorative material according to claim 7, wherein the intermediate resinlayer is in contact with the surface protective layer.